U.S. patent number 10,875,283 [Application Number 15/329,890] was granted by the patent office on 2020-12-29 for adhesive layer-equipped laminate, and flexible copper-clad laminate sheet and flexible flat cable using same.
This patent grant is currently assigned to TOAGOSEI CO., LTD.. The grantee listed for this patent is TOAGOSEI CO., LTD.. Invention is credited to Yuya Okimura, Masashi Yamada.
United States Patent |
10,875,283 |
Okimura , et al. |
December 29, 2020 |
Adhesive layer-equipped laminate, and flexible copper-clad laminate
sheet and flexible flat cable using same
Abstract
A laminate having an adhesive layer, which exhibits excellent
adhesion to base films made from polyimide resins and the like or
copper foils, as well as superior electrical properties, and also
providing a laminate having an adhesive layer, which is low in
warpage when the adhesive layer is in B stage, and which is
excellent in storage stability of the laminate. The laminate having
an adhesive layer includes a base film and an adhesive layer formed
on at least one of the surfaces of the base film, in which the
adhesive layer is formed of an adhesive composition comprising a
carboxyl group-containing styrene based elastomer and an epoxy
resin, wherein the content of the carboxyl group-containing styrene
based elastomer is 50 parts by mass or more relative to 100 parts
by mass of the solid content of the adhesive composition; the
content of the epoxy resin is from 1 to 20 parts by mass relative
to 100 parts by mass of the carboxyl group-containing styrene based
elastomer; and the adhesive layer is in B-stage.
Inventors: |
Okimura; Yuya (Nagoya,
JP), Yamada; Masashi (Nagoya, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
TOAGOSEI CO., LTD. |
Tokyo |
N/A |
JP |
|
|
Assignee: |
TOAGOSEI CO., LTD. (Tokyo,
JP)
|
Family
ID: |
1000005267543 |
Appl.
No.: |
15/329,890 |
Filed: |
July 21, 2015 |
PCT
Filed: |
July 21, 2015 |
PCT No.: |
PCT/JP2015/070694 |
371(c)(1),(2),(4) Date: |
January 27, 2017 |
PCT
Pub. No.: |
WO2016/017473 |
PCT
Pub. Date: |
February 04, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20170259544 A1 |
Sep 14, 2017 |
|
Foreign Application Priority Data
|
|
|
|
|
Jul 31, 2014 [JP] |
|
|
2014-156726 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B
15/09 (20130101); B32B 15/08 (20130101); B32B
27/38 (20130101); B32B 27/00 (20130101); B32B
27/286 (20130101); C08L 53/025 (20130101); B32B
27/281 (20130101); B32B 27/34 (20130101); B32B
7/12 (20130101); B32B 27/32 (20130101); H05K
1/0353 (20130101); H05K 3/386 (20130101); C08L
25/06 (20130101); H05K 1/09 (20130101); B32B
27/288 (20130101); B32B 7/06 (20130101); B32B
27/08 (20130101); B32B 27/36 (20130101); B32B
15/12 (20130101); B32B 25/08 (20130101); C09J
7/35 (20180101); B32B 15/20 (20130101); B32B
27/10 (20130101); C08L 63/00 (20130101); B32B
15/088 (20130101); C09J 125/06 (20130101); B32B
27/28 (20130101); B32B 15/085 (20130101); C09J
163/00 (20130101); H05K 1/028 (20130101); C09J
153/025 (20130101); C09J 153/025 (20130101); C08L
25/06 (20130101); C08L 63/00 (20130101); C09J
125/06 (20130101); C08L 53/025 (20130101); C08L
63/00 (20130101); C09J 153/025 (20130101); C08L
63/00 (20130101); B32B 2255/12 (20130101); B32B
2309/105 (20130101); H05K 2201/0154 (20130101); C09J
2400/163 (20130101); C09J 2453/00 (20130101); C09J
2479/086 (20130101); C09J 2203/326 (20130101); H05K
3/022 (20130101); B32B 2457/08 (20130101); C09J
2425/00 (20130101); B32B 2307/732 (20130101); B32B
2307/204 (20130101); B32B 2307/546 (20130101); B32B
2307/748 (20130101); H05K 2201/0158 (20130101); C09J
2301/414 (20200801); C09J 2463/00 (20130101); B32B
2255/10 (20130101); B32B 2255/26 (20130101); C09J
125/10 (20130101); C09J 2425/00 (20130101); C09J
2463/00 (20130101); C09J 2453/00 (20130101); C09J
2463/00 (20130101) |
Current International
Class: |
B32B
27/38 (20060101); H05K 1/09 (20060101); H05K
1/03 (20060101); H05K 1/02 (20060101); B32B
27/32 (20060101); B32B 7/12 (20060101); B32B
7/06 (20190101); B32B 15/088 (20060101); B32B
27/36 (20060101); B32B 27/08 (20060101); B32B
15/09 (20060101); B32B 15/20 (20060101); B32B
27/10 (20060101); B32B 15/085 (20060101); C09J
163/00 (20060101); B32B 27/00 (20060101); B32B
25/08 (20060101); B32B 15/08 (20060101); C09J
125/06 (20060101); C08L 63/00 (20060101); C09J
7/35 (20180101); H05K 3/38 (20060101); C09J
153/02 (20060101); C08L 53/02 (20060101); C08L
25/06 (20060101); B32B 15/12 (20060101); B32B
27/28 (20060101); B32B 27/34 (20060101); H05K
3/02 (20060101); C09J 125/10 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2652978 |
|
Nov 2007 |
|
CA |
|
1715353 |
|
Jan 2006 |
|
CN |
|
H10-7996 |
|
Jan 1998 |
|
JP |
|
2002-88332 |
|
Mar 2002 |
|
JP |
|
2006-9015 |
|
Jan 2006 |
|
JP |
|
2007-2121 |
|
Jan 2007 |
|
JP |
|
2007-51195 |
|
Mar 2007 |
|
JP |
|
2009-537689 |
|
Oct 2009 |
|
JP |
|
2011-68713 |
|
Apr 2011 |
|
JP |
|
2006/090715 |
|
Aug 2006 |
|
WO |
|
2012/011265 |
|
Jan 2012 |
|
WO |
|
Other References
English language machine translation of JP 2002-088332 (Year:
2002). cited by examiner .
English language machine translation of JP 2007-002121 (Year:
2007). cited by examiner .
International Search Report for PCT/JP2015/070694 dated Oct. 20,
2015; English translation submitted herewith (4 pages). cited by
applicant .
JPO Office Action apparently dated Jan. 15, 2019 issued in JP
Patent Application No. 2018-086615. cited by applicant .
JPO Office Action apparently dated Jan. 15, 2019 issued in JP
Patent Application No. 2018-08618. cited by applicant .
JPO Office Action apparently dated Jan. 16, 2019 issued in JP
Patent Application No. 2016-538280. cited by applicant .
Taiwan PO Office Action apparently dated Jan. 24, 2019 issued
apparently in TW Application No. 104124324. cited by applicant
.
Office Action issued against corresponding Chinese Patent
Application No. 201580040206.X, apparently dated Jun. 3, 2020 (5
pages). cited by applicant .
SIPO, First Office Action, apparently dated Aug. 5, 2019, issued re
PRC application 201580040206.X. cited by applicant .
SIPO, Second Office Action, apparently dated Mar. 12, 2020, issued
re PRC application 201580040206.X. cited by applicant .
JPCA Standard, Flexible Printed Wiring Boards and Material for
Flexible Printed Wiring Boards--Part II Integrated Standard--,
JPCA-DG04-2012, dated Dec. 2011, published by Japan Electronics
Packaging and Circuits Association; partial English translation
(129 pages). cited by applicant .
JPCA Standard, Text methods of copper-clad laminates for flexible
printed wiring boards, JPCA-TM0002-2009, dated Jun. 2009, by Japan
Electronics Packaging and Circuits Association; partial English
translation (41 pages). cited by applicant.
|
Primary Examiner: McCulley; Megan
Attorney, Agent or Firm: Fitch, Even, Tabin & Flannery,
LLP
Claims
The invention claimed is:
1. A laminate having an adhesive layer, which comprises a base
film; and an adhesive layer formed on at least one of the surfaces
of the base film, wherein the adhesive layer is formed of an
adhesive composition comprising (A) a carboxyl group-containing
styrene-based elastomer, (B) an epoxy resin, and (C) a curing
accelerator, with the proviso the adhesive composition has no epoxy
resin having a glycidylamino group, wherein the content of the
carboxyl group-containing styrene-based elastomer (A) is 50 parts
by mass or more relative to 100 parts by mass of the solid content
of the adhesive composition, the content of the epoxy resin (B) is
1 to 20 parts by mass relative to 100 parts by mass of the carboxyl
group-containing styrene-based elastomer (A), the adhesive layer is
in B-stage, and the carboxyl group-containing styrene-based
elastomer (A) has an acid value of from 0.1 to 25 mg KOH/g.
2. The laminate having an adhesive layer according to claim 1,
wherein the adhesive layer is formed by coating a resin varnish
comprising the adhesive composition and a solvent on a surface of
the base film to form a resin varnish layer, and then removing the
solvent from the resin varnish layer.
3. The laminate having an adhesive layer according to claim 1,
wherein the laminate has a ratio (H/L) of less than 0.05, wherein H
is an elevation of an edge of the laminate and L is a side length
of the laminate when the laminate having an adhesive layer is
square-shaped and placed on a horizontal surface with the adhesive
layer facing up.
4. The laminate having an adhesive layer according claim 1, wherein
the base film is at least one film selected from the group
consisting of a polyimide film, a polyether ether ketone film, a
polyphenylene sulfide film, an aramid film, a polyethylene
naphthalate film, a liquid crystal polymer film, a polyethylene
terephthalate film, a polyethylene film, a polypropylene film, a
silicone-treated release paper, a polyolefin resin-coated paper, a
TPX film, and a fluororesin film.
5. The laminate having an adhesive layer according to claim 1,
wherein the base film has a thickness from 5 to 100 .mu.m.
6. The laminate having an adhesive layer according to claim 1,
wherein the carboxyl group-containing styrene-based elastomer (A)
is obtained by modifying at least one styrene-based elastomer
selected from the group consisting of styrene-butadiene block
copolymers, styrene-ethylenepropylene block copolymers,
styrene-butadiene-styrene block copolymers,
styrene-isoprene-styrene block copolymers,
styrene-ethylenebutylene-styrene block copolymers, and
styrene-ethylenepropylene-styrene block copolymers with an
unsaturated carboxylic acid.
7. The laminate having an adhesive layer according to claim 1,
wherein the epoxy resin (B) is a multifunctional epoxy resin having
an alicyclic structure.
8. The laminate having an adhesive layer according to claim 7,
wherein the alicyclic structure is a dicyclopentadiene
structure.
9. The laminate having an adhesive layer according to claim 1,
wherein the adhesive layer has a thickness of from 5 to 100
.mu.m.
10. The laminate having an adhesive layer according to claim 1,
wherein the adhesive layer has a thickness equal to or thicker than
the thickness of the base film.
11. The laminate having an adhesive layer according to claim 1,
wherein said laminate exhibits a dielectric constant lower than 3.0
and a dielectric loss tangent lower than 0.01, as measured at a
frequency of 1 GHz after curing the adhesive layer.
12. A flexible copper clad laminate which comprises a laminate
according to claim 1 and a copper foil bonded onto the adhesive
layer of the laminate.
13. A flexible flat cable which comprises a laminate according to
claim 1 and a copper wiring bonded onto the adhesive layer of the
laminate.
14. The laminate having an adhesive layer according to claim 1,
wherein the base film is at least one film selected from the group
consisting of a polyimide film, a polyether ether ketone film, a
polyphenylene sulfide film, an aramid film, a polyethylene
naphthalate film, a liquid crystal polymer film, a polyethylene
terephthalate film, a polyethylene film, a polypropylene film, a
silicone-treated release paper, a polyolefin resin-coated paper, a
TPX film, and a fluororesin film; wherein the base film has a
thickness of from 5 to 100 .mu.m; wherein the adhesive layer has a
thickness of from 5 to 100 .mu.m that is equal to or greater than
the thickness of the base film; and wherein the laminate has a
ratio (H/L) of less than 0.05, in which H is an elevation of an
edge of the laminate and L is a side length of the laminate when
the laminate having an adhesive layer is square-shaped and placed
on a horizontal surface with the adhesive layer facing up.
15. The laminate having an adhesive layer according to claim 1,
wherein the carboxyl group-containing styrene-based elastomer (A)
has an acid value of from 0.5 to 23 mg KOH/g.
16. The laminate having an adhesive layer according to claim 1,
wherein the carboxyl group-containing styrene-based elastomer (A)
has an acid value of 0.1 mg KOH/g to 10 mg KOH/g.
17. The laminate having an adhesive layer according to claim 1,
wherein the carboxyl group-containing styrene-based elastomer (A)
has an acid value of 0.5 mg KOH/g to 10 mg KOH/g.
18. The laminate having an adhesive layer according to claim 1,
wherein the content of the curing accelerator is 1 to 10 parts by
mass relative to 100 parts by mass of the epoxy resin (B).
19. The laminate having an adhesive layer according to claim 1,
wherein the content of the curing accelerator is 2 to 5 parts by
mass relative to 100 parts by mass of the epoxy resin (B).
20. The laminate having an adhesive layer according to claim 1,
wherein the curing accelerator comprises a tertiary amine-based
curing accelerator, tertiary amine salt-based curing accelerator,
or an imidazole-based curing accelerator.
21. The laminate having an adhesive layer according to claim 1,
wherein the curing accelerator comprises a tertiary amine-based
curing accelerator.
22. The laminate having an adhesive layer according to claim 1,
wherein the curing accelerator comprises a tertiary amine
salt-based curing accelerator.
23. The laminate having an adhesive layer according to claim 1,
wherein the curing accelerator comprises imidazole-based curing
accelerator.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national phase application filed under
35 U.S.C. .sctn. 371 of International Application No.
PCT/JP2015/070694, filed Jul. 21, 2015, designating the United
States, which claims priority from Japanese Patent Application No.
2014-156726, filed Jul. 21, 2014, and the complete disclosures of
which applications are hereby incorporated herein by reference in
their entirety for all purposes.
TECHNICAL FIELD
The present invention relates to a laminate having an adhesive
layer. In further detail, it relates to a laminate having an
adhesive layer, which is suitable for use in bonding electronic
parts and the like, particularly for manufacturing products related
to flexible printed circuits (hereinafter simply referred to as
"FPC").
BACKGROUND ART
As electronic devices become more compact and lightweight, the need
for bonding electronic parts and the like is diversifying and the
demand for the laminate having an adhesive layer is increasing. For
instance, as the products related to FPC which is one of the
electronic parts, there can be mentioned a flexible copper clad
laminate in which a copper foil is bonded to a polyimide film; a
flexible printed circuit in which an electronic circuit is formed
on the flexible copper clad laminate; a reinforced flexible printed
circuit in which the flexible printed circuit is bonded to a
reinforcing board; a multilayered board having the flexible copper
clad laminate layered on and bonded to the flexible printed circuit
board; a flexible flat cable (hereinafter simply referred to as
"FFC") comprising copper wiring bonded to a base film, and the
like. When these electronic parts are manufactured, the laminate
having an adhesive layer is used.
More specifically, when the FPC is manufactured, a "coverlay film"
which is a laminate having an adhesive layer is generally used for
protecting wired portions. The coverlay film consists of an
insulating resin layer and an adhesive layer formed thereon, and a
polyimide resin composition is widely used for forming the
insulating resin layer. In manufacturing the flexible printed
circuits, the coverlay film is bonded to the surface having wired
portions thereon via the adhesive layer by use of, for instance, a
heat press. In this instance, the adhesive layer of the coverlay
film is required to establish a strong adhesion to both the wired
portions and the base film.
As adhesives for use in the FPC related products, there have been
proposed epoxy-based adhesive compositions containing a
thermoplastic resin highly reactive with the epoxy resin. For
instance, Patent Document 1 discloses an adhesive sheet having an
adhesive layer formed of an adhesive composition comprising a
carboxylic acid-modified block copolymer, an epoxy compound having
a glycidylamino group and at least three epoxy groups in molecule,
and an epoxy resin having two or more epoxy groups in molecule.
Furthermore, Patent Document 2 discloses a coverlay film having an
adhesive layer formed of an adhesive that is based on a
styrene-maleic acid copolymer and an epoxy resin.
Furthermore, in the field of mobile communication equipment such as
mobile phones and information terminal devices which are now
rapidly increasing in demand, higher frequency signals are used to
process a huge amount of data at high speed. Accordingly, with the
increase in signal speed and signal frequency, the adhesive for use
in FPC-related products must satisfy electrical properties in the
high frequency region (i.e, low dielectric constant and low
dielectric loss tangent). To cope with such demands in electrical
properties, for example, Patent Document 3 discloses a coverlay
film comprising a vinyl compound, a
polystyrene-poly(ethylene/butylene) block copolymer, an epoxy
resin, and a curing catalyst.
CONVENTIONAL TECHNICAL DOCUMENTS
Patent Documents
Patent Document 1: Japanese Patent Publication (Laid-open) No.
2002-88332. Patent Document 2: Japanese Patent Publication
(Laid-open) No. 2007-2121. Patent Document 3: Japanese Patent
Publication (Laid-open) No. 2011-68713.
SUMMARY OF INVENTION
Problems to be Solved by the Invention
However, the thermosetting adhesive sheet disclosed in Patent
Document 1 is problematic in that it is inferior in storage
stability in the adhesive sheet state. The coverlay film disclosed
in Patent Document 2 is still unsatisfactory because the electrical
properties in the ultra high frequency microwave region (1 to 3
GHz) are poor. Furthermore, the coverlay film disclosed in Patent
Document 3 sometimes warps before thermosetting (in B stage), and
it therefore suffers from the problem of bad workability during the
FPC production process. A thinner base film is required to improve
the electrical properties, however, even when the base film is made
thinner, it is still desired that the warpage of the laminate
having the adhesive layer is suppressed.
The present invention has been made in light of the above described
problems, and aims at providing a laminate having an adhesive
layer, which exhibits a strong adhesion to base films made from
polyimide resins and the like or copper foils, while exhibiting
superior electrical properties. Another objective is to provide a
laminate having an adhesive layer, which is low in warpage when the
adhesive layer is in B stage, and which is excellent in storage
stability of the laminate.
Means for Solving the Problems
The present inventors have found that a laminate having an adhesive
layer, which comprises a base film and an adhesive layer, exhibits
not only excellent adhesiveness but also little warpage and
excellent storage stability when the adhesive layer is formed of an
adhesive composition containing specific amounts of a carboxyl
group-containing styrene based elastomer and an epoxy resin, and
further is in B-stage. The present invention has been accomplished
based on these findings.
Thus, a laminate having an adhesive layer according to the present
invention and a flexible copper clad laminate using the same are
described as follows.
1. A laminate having an adhesive layer, which comprises a base film
and an adhesive layer formed on at least one of the surfaces of the
base film, in which the adhesive layer is formed of an adhesive
composition comprising a carboxyl group-containing styrene based
elastomer (A) and an epoxy resin (B), wherein the content of the
carboxyl group-containing styrene based elastomer (A) is 50 parts
by mass or more relative to 100 parts by mass of the solid content
of the adhesive composition, the content of the epoxy resin (B) is
1 to 20 parts by mass relative to 100 parts by mass of the carboxyl
group-containing styrene based elastomer (A), and the adhesive
layer is in B-stage.
2. The laminate having an adhesive layer, according to the above
item 1, wherein the adhesive layer is formed by coating a resin
varnish comprising the aforementioned adhesive composition and a
solvent on a surface of the base film to form a resin varnish
layer, and then removing the solvent from the resin varnish
layer.
3. The laminate having an adhesive layer, according to the above
items 1 or 2, which has a ratio (H/L) of less than 0.05 wherein H
is an elevation of an edge of the laminate and L is a side length
of the laminate when the laminate having an adhesive layer is
square-shaped and placed on a horizontal surface with the adhesive
layer facing up.
4. The laminate having an adhesive layer, according to any one of
the above items 1 to 3, wherein the base film is at least one film
selected from the group consisting of a polyimide film, a polyether
ether ketone film, a polyphenylene sulfide film, an aramid film, a
polyethylene naphthalate film, a liquid crystal polymer film, a
polyethylene terephthalate film, a polyethylene film, a
polypropylene film, a silicone-treated release paper, a polyolefin
resin-coated paper, a TPX film, and a fluororesin film.
5. The laminate having an adhesive layer, according to any one of
the above items 1 to 4, wherein the thickness of the base film is 5
to 100 .mu.m.
6. The laminate having an adhesive layer, according to any one of
the above items 1 to 5, wherein the acid value of the carboxyl
group-containing styrene based elastomer (A) is 0.1 to 25 mg
KOH/g.
7. The laminate having an adhesive layer, according to any one of
the above items 1 to 6, wherein the carboxyl group-containing
styrene based elastomer (A) is obtained by modifying at least one
styrene-based elastomer selected from the group consisting of
styrene-butadiene block copolymers, styrene-ethylenepropylene block
copolymers, styrene-butadiene-styrene block copolymers,
styrene-isoprene-styrene block copolymers,
styrene-ethylenebutylene-styrene block copolymers, and
styrene-ethylenepropylene-styrene block copolymers with an
unsaturated carboxylic acid.
8. The laminate having an adhesive layer, according to any one of
the above items 1 to 7, wherein the epoxy resin (B) is an epoxy
resin having no glycidylamino group.
9. The laminate having an adhesive layer, according to any one of
the items 1 to 8, wherein the epoxy resin (B) is a multifunctional
epoxy resin having an alicyclic structure.
10. The laminate having an adhesive layer, according to any one of
the above items 1 to 9, wherein the thickness of the adhesive layer
is 5 to 100 .mu.m.
11. The laminate having an adhesive layer, according to any one of
the above items 1 to 10, wherein the thickness of the adhesive
layer is equal to or thicker than the thickness of the base
film.
12. The laminate having an adhesive layer, according to any one of
the above items 1 to 11, which exhibits a dielectric constant lower
than 3.0 and a dielectric loss tangent lower than 0.01, as measured
at a frequency of 1 GHz after curing the adhesive layer.
13. A flexible copper clad laminate which comprises a laminate
having an adhesive layer according to any one of the above items 1
to 12 and a copper foil bonded onto the adhesive layer of the
laminate.
14. A flexible flat cable which comprises a laminate having an
adhesive layer according to any one of the above items 1 to 12 and
a copper wiring bonded onto the adhesive layer of the laminate.
Effect of the Invention
The laminate having an adhesive layer according to the present
invention is excellent in adhesion to base films made from
polyimide resins and the like or copper foils, resin flow, and
electrical properties (such as low dielectric constant and low
dielectric loss tangent). The present laminate having the adhesive
layer shows little warpage, and thus exhibits excellent workability
in the manufacturing processes of various types of components, and
favorable storage stability of the laminates. Accordingly, the
laminate having the adhesive layer of the present invention is
suitable for manufacture and the like of the FPC-related
products.
DESCRIPTION OF EMBODIMENTS
Embodiments of the present invention will be explained below;
however, the present invention is not limited thereto.
1. Laminate Having an Adhesive Layer
The laminate having an adhesive layer according to the present
invention comprises a base film and an adhesive layer formed on at
least one of the surfaces of the base film, in which the adhesive
layer is formed of an adhesive composition comprising specific
amounts of a carboxyl group-containing styrene based elastomer (A)
and an epoxy resin (B), and the adhesive layer is in B-stage.
Specific matters that define the present invention are described in
detail below.
(1) Base Film
The base film used in the present invention can be selected
depending on the usage of the laminate having an adhesive layer.
When the laminate having an adhesive layer is used as a coverlay
film, examples of the base film include a polyimide film, a
polyether ether ketone film, a polyphenylene sulfide film, an
aramid film, a polyethylene naphthalate film, and a liquid crystal
polymer film. Preferred among them from the viewpoint of
adhesiveness and electrical properties are a polyimide film, a
polyethylene naphthalate film, and a liquid crystal polymer
film.
The aforementioned base films are commercially available; for
instance, examples of the polyimide film include "KAPTON
(registered trademark)" manufactured by Du Pont Toray Co., Ltd.,
"XENOMAX (registered trademark)" manufactured by Toyobo Co., Ltd.,
"UPILEX (registered trademark)-S" manufactured by Ube Industries,
Ltd., and "APICAL (registered trademark)" manufactured by Kaneka
Corporation. Examples of the polyethylene naphthalate film include
"TEONEX (registered trademark)" manufactured by Teijin DuPont Films
Japan Limited. Furthermore, examples of the liquid crystal polymer
film include "VECSTAR (registered trademark)" manufactured by
Kurary Co., Ltd, and "BIAC (registered trademark)" manufactured by
Primatec Co., Ltd. The base film can also be obtained by making a
film of desired thickness from the corresponding resin.
When the laminate having an adhesive layer according to the present
invention is used as a bonding sheet, the base film should be a
release film such as a polyethylene terephthalate film, a
polyethylene film, a polypropylene film, a silicone-treated release
paper, a polyolefin resin-coated paper, a TPX (polymethylpentene)
film, and a fluororesin film.
Such release films are commercially available, and examples thereof
include "LUMIRROR (registered trademark)" manufactured by Toray
Industries, Inc., "TOYOBO ESTER (registered trademark) film"
manufactured by Toyobo Co., Ltd., "AFLEX (registered trademark)"
manufactured by Asahi Glass Co., Ltd., and "OPULENT (registered
trademark)" manufactured by Mitsui Chemicals Tohcello. Inc.
In order to make thinner the laminate having the adhesive layer,
the thickness of the base film is preferably from 5 to 100 nm, more
preferably from 5 to 50 nm, and still more preferably from 5 to 30
nm.
(2) Adhesive Layer
The adhesive layer for use in the laminate according to the present
invention is formed of an adhesive composition comprising a
carboxyl group-containing styrene based elastomer (A) and an epoxy
resin (B), wherein the content of the carboxyl group-containing
styrene based elastomer (A) is 50 parts by mass or more relative to
100 parts by mass of the solid content of the adhesive composition;
the content of the epoxy resin (B) is from 1 to 20 parts by mass
relative to 100 parts by mass of the carboxyl group-containing
styrene based elastomer (A); and the adhesive layer is in
B-stage.
The above carboxyl group-containing styrene based elastomer (A) is
one of the main components of the adhesive composition and provides
not only adhesiveness and flexibility of cured products but also
electrical properties. The carboxyl group-containing styrene based
elastomer is one obtained by modifying, with an unsaturated
carboxylic acid, copolymers mainly constituted by block and random
structures of conjugated diene compounds and aromatic vinyl
compounds, or hydrogenated products thereof. Specific examples of
the aromatic vinyl compounds include styrene, t-butylstyrene,
.alpha.-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylstyrene, N,N-diethyl-p-aminoethylstyrene, vinyltoluene,
and p-tert-butylstyrene. Examples of the conjugated diene compounds
include butadiene, isoprene, 1,3-pentadiene, and
2,3-dimethyl-1,3-butadiene.
The modification of the carboxyl group-containing styrene based
elastomer (A) can be conducted, for instance, by copolymerizing an
unsaturated carboxylic acid when a styrene-based elastomer is
polymerized. Otherwise, the styrene-based elastomer can be heated
and kneaded together with an unsaturated carboxylic acid in the
presence of an organic peroxide. Examples of the unsaturated
carboxylic acid include acrylic acid, methacrylic acid, maleic
acid, itaconic acid, fumaric acid, maleic anhydride, itaconic
anhydride, and fumaric anhydride. The amount of the unsaturated
carboxylic acid to be used for the modification is preferably from
0.1 to 10 mass %.
The acid value of the carboxyl group-containing styrene based
elastomer (A) is preferably from 0.1 to 25 mg KOH/g, and more
preferably from 0.5 to 23 mg KOH/g. When the acid value is 0.1 mg
KOH/g or more, the adhesive composition can be cured sufficiently
to achieve excellent adhesiveness, heat resistance, and resin flow.
When the acid value is 25 mg KOH/g or less, excellent adhesion
strength and electrical properties can be realized.
The weight average molecular weight of the carboxyl
group-containing styrene based elastomer (A) is preferably from 1
to 500,000, more preferably from 3 to 300,000, and still more
preferably from 5 to 200,000. When the weight average molecular
weight is in the range of from 1 to 500,000, excellent adhesiveness
and electrical properties can be exhibited. In the present
description, "weight average molecular weight" refers to a
molecular weight value determined by gel permeation chromatography
(hereinafter referred to as "GPC") with calibration using
polystyrene standards.
Specific examples of the carboxyl group-containing styrene based
elastomer (A) include those obtained by modifying, with an
unsaturated carboxylic acid, styrene-butadiene block copolymers,
styrene-ethylenepropylene block copolymers,
styrene-butadiene-styrene block copolymers,
styrene-isoprene-styrene block copolymers,
styrene-ethylenebutylene-styrene block copolymers,
styrene-ethylenepropylene-styrene block copolymers, and the like.
These carboxyl group-containing styrene based elastomers can be
used alone or in combination of two or more. Among the
aforementioned copolymers, preferred from the viewpoint of
adhesiveness and electrical properties are
styrene-ethylenebutylene-styrene block copolymers and
styrene-ethylenepropylene-styrene block copolymers. Furthermore,
the mass ratio of styrene/ethylenebutylene in the
styrene-ethylenebutylene-styrene block copolymers and the mass
ratio of styrene/ethylenepropylene in the
styrene-ethylenepropylene-styrene block copolymers are preferably
in from 10/90 to 50/50 and more preferably from 20/80 to 40/60. The
adhesive composition with the mass ratio in this range exhibits
excellent adhesive properties.
The content of the carboxyl group-containing styrene based
elastomer (A) should be 50 parts by mass or more, and preferably 60
parts by mass or more, relative to 100 parts by mass of the solid
content of the adhesive composition. When the content is less than
50 parts by mass, the adhesive layer lacks flexibility and causes
warping of the laminate.
The content of the carboxyl group-containing styrene based
elastomer (A) is preferably 99 parts by mass or less relative to
100 parts by mass of the solid content of the adhesive
composition.
Hereinafter, explanation of another component in the above adhesive
composition, i.e., epoxy resin (B), is given. The epoxy resin (B)
reacts with the carboxyl group of the above carboxyl
group-containing styrene based elastomer (A) to realize high
adhesion to adherends and heat resistance of cured products of the
adhesive.
Examples of the epoxy resin (B) include, but are not limited to, a
bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a
hydrogenated product thereof; glycidyl ester type epoxy resins such
as diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl
terephthalate, glycidyl p-hydroxybenzoate, diglycidyl
tetrahydrophthalate, diglycidyl succinate, diglycidyl adipate,
diglycidyl sebacate, and triglycidyl trimellitate; glycidyl ether
type epoxy resins such as ethylene glycol diglycidyl ether,
propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether,
1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl
ether, pentaerythritol tetraglycidyl ether,
tetraphenylglycidylether ethane, triphenylglycidylether ethane,
polyglycidyl ethers of sorbitol, and polyglycidyl ethers of
polyglycerol; glycidylamine type epoxy resins such as triglycidyl
isocyanurate and tetraglycidyl diaminodiphenylmethane; and linear
aliphatic epoxy resins such as epoxidized polybutadiene and
epoxidized soybean-oil. Also usable are novolac type epoxy resins
such as phenol novolac epoxy resin, o-cresol novolac epoxy resin
and bisphenol A novolac epoxy resin.
Furthermore, examples of the epoxy resins include a brominated
bisphenol A type epoxy resin, a phosphorus-containing epoxy resin,
an epoxy resin having dicyclopentadiene structure, an epoxy resin
having naphthalene structure, an anthracene type epoxy resin, a
tertiary butylcatechol type epoxy resin, a triphenylmethane type
epoxy resin, a tetraphenylethane type epoxy resin, a biphenyl type
epoxy resin, and a bisphenol S type epoxy resin. These epoxy resins
may be used alone or in combination of two or more.
Among the above epoxy resins, preferred are those having no
glycidylamino group because the storage stability of the laminate
having an adhesive layer can be improved. Furthermore, because an
adhesive composition having excellent electrical properties can be
obtained, preferred are epoxy resins having an aliphatic cyclic
structure, and more preferred are epoxy resins having a
dicyclopentadiene structure.
The epoxy resin for use in the present invention is preferably one
having two or more epoxy groups per one molecule, because it reacts
with the carboxyl-group containing styrene based elastomer to form
a crosslinking structure and realize high thermal resistance. When
an epoxy resin having two or more epoxy groups is used, sufficient
crosslinking with the carboxyl group-containing styrene based
elastomer is formed to establish sufficient thermal resistance.
The content of the epoxy resin (B) should be from 1 to 20 parts by
mass relative to 100 parts by mass of the above carboxyl
group-containing styrene based elastomer (A). Preferably, the
content is from 3 to 15 parts by mass. If the content is less than
1 parts by mass, sufficient adhesiveness or thermal resistance may
not be obtained. On the other hand, if the content exceeds 20 parts
by mass, peel adhesion strength or electrical properties may be
impaired.
In addition to the carboxyl group-containing styrene based
elastomer (A) and the epoxy resin (B), the above adhesive
composition may contain, for instance, a thermoplastic resin other
than the carboxyl group-containing styrene based elastomer (A), a
tackifier, a flame retardant, a curing agent, a curing accelerator,
a coupling agent, an anti-thermal aging agent, a leveling agent, an
antifoaming agent, an inorganic filler, a pigment, and a solvent in
amounts not affecting the function of the adhesive composition.
Examples of the above other thermoplastic resins include phenoxy
resins, polyamide resins, polyester resins, polycarbonate resins,
polyphenylene oxide resins, polyurethane resins, polyacetal resins,
polyethylene resins, polypropylene resins, and polyvinyl resins.
These thermoplastic resins may be used either alone or in
combination of two or more.
Examples of the above tackifiers include coumarone-indene resins,
terpene resins, terpene-phenol resins, rosin resins,
p-t-butylphenol-acetylene resins, phenol-formaldehyde resins,
xylene-formaldehyde resins, petroleum-based hydrocarbon resins,
hydrogenated hydrocarbon resins, and turpentine-based resins. These
tackifiers may be used alone or in combination of two or more.
The flame retardant may be either an organic flame retardant or an
inorganic flame retardant. Examples of organic flame retardants
include phosphorus based flame retardants such as melamine
phosphate, melamine polyphosphate, guanidine phosphate, guanidine
polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium
phosphate amide, ammonium polyphosphate amide, carbamoyl phosphate,
carbamoyl polyphosphate, aluminum trisdiethylphosphinate, aluminum
trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc
bis diethylphosphinate, zinc bismethylethylphosphinate, zinc bis
diphenylphosphinate, titanyl bisdiethylphosphinate, titanium
tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate,
titanium tetrakismethylethylphosphinate, titanyl bis
diphenylphosphinate, and titanium tetrakisdiphenylphosphinate;
nitrogen based flame retardants which includes triazine compounds
such as melamine, melam, and melamine cyanurate, cyanuric acid
compounds, isocyanuric acid compounds, triazole compounds,
tetrazole compounds, diazo compounds, and urea; and silicon based
flame retardants such as silicone compounds and silane compounds.
Examples of the inorganic flame retardants include metal hydroxides
such as aluminum hydroxide, magnesium hydroxide, zirconium
hydroxide, barium hydroxide, and calcium hydroxide; metal oxides
such as tin oxide, aluminum oxide, magnesium oxide, zirconium
oxide, zinc oxide, molybdenum oxide, and nickel oxide; zinc
carbonate, magnesium carbonate, barium carbonate, zinc borate, and
hydrated glass. These flame retardants may be used in combination
of two or more.
Examples of the above curing agents include, but not limited
thereto, amine-based curing agents and acid anhydride-based curing
agents. Amine-based curing agents include, for instance, melamine
resins such as methylated melamine resin, butylated melamine resin,
and benzoguanamine resin; dicyandiamide, and
4,4'-diphenyldiaminosulfone. Acid anhydrides include, for example,
aromatic acid anhydrides and aliphatic acid anhydrides. These
curing agents may be used alone or in combination of two or
more.
The content of the curing agent is preferably from 1 to 100 parts
by mass, more preferably from 5 to 70 parts by mass, relative to
100 parts by mass of the epoxy resin (B).
The above curing accelerator is used for the purpose of
accelerating the reaction of the carboxyl group-containing styrene
based elastomer and the epoxy resin. Usable as the curing
accelerator are tertiary amine-based curing accelerator, tertiary
amine salt based curing accelerator, and imidazole based curing
accelerator.
Examples of the tertiary amine-based curing accelerator include
benzyldimethylamine, 2-(dimethylaminomethyl)phenol,
2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine,
triethanolamine, N,N'-dimethylpiperadine, triethylenediamine, and
1,8-diazabicyclo[5.4.0] undecene.
Examples of the tertiary amine salt based curing accelerator
include a formic acid salt, an octylic acid salt, a
p-tofuenesulfonic acid salt, an o-phthalic acid salt, a phenol salt
or a phenol novolac resin salt of 1,8-diazabicyclo[5.4.0] undecene,
as well as a formic acid salt, an octylic acid salt, a
p-toluenesulfonic acid salt, an o-phthalic acid salt, a phenol salt
or a phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]
nonene.
Examples of the imidazole based curing accelerator include
2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,
1,2-dimethylimidazole, 2-methyl-4-ethylimidazole,
2-phenylimidazole, 2-phenyl-4-methylimidazole,
1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole,
2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine,
2,4-diamino-6-[2'-undecylimidazolyl-(1')]ethyl-s-triazine,
2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine,
2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine
isocyanurate adduct, 2-phenylimidazole isocyanurate adduct,
2-phenyl-4,5-dihydroxymethylimidazole, and
2-phenyl-4-methyl-5-hydroxymethylimidazole. These curing
accelerators may be used alone or in combination of two or
more.
When the curing accelerator is contained in the adhesive
composition, the content of the curing accelerator is preferably 1
to 10 parts by mass, more preferably 2 to 5 parts by mass, relative
to 100 parts by mass of the epoxy resin (B). Excellent adhesiveness
and thermal resistance can be exhibited so long as the content of
the curing accelerator is in the aforementioned range.
Examples of the coupling agents include silane-based coupling
agents such as vinyltrimethoxysilane,
3-glycydoxypropyltrimethoxysilane, p-styryltrimethoxysilane,
3-methacryloxypropylmethyldimethoxysilane,
3-acryloxypropyltrimethoxysilane,
N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,
3-ureidopropyltriethoxysilane,
3-mercaptopropylmethyldimethoxysilane,
bis(triethoxysilylpropyl)tetrasulfide,
3-isocyanatopropyltriethoxysilane, and imidazolesilane;
titanate-based coupling agents, aluminate-based coupling agents,
and zirconium-based coupling agents. These may be used alone or in
combination of two or more.
Examples of the anti-thermal aging agents include phenol-based
antioxidants such as 2,6-di-tert-butyl-4-methylphenol,
n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate,
tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methan-
e, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenol,
and triethylene glycol
bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate;
sulfur-based antioxidants such as dilauryl 3,3'-thiodipropionate,
and dimyristyl 3,3'-dithiopropionate; and phosphorus-based
antioxidants such as tris(nonylphenyl) phosphite, and
tris(2,4-di-tert-butylphenyl) phosphite. These may be used alone or
in combination of two or more.
Examples of the inorganic fillers include powders of titanium
oxide, aluminum oxide, zinc oxide, carbon black, silica, talc,
copper, and silver. These may be used alone or in combination of
two or more.
The adhesive composition can be produced by mixing the carboxyl
group-containing styrene based elastomer (A), the epoxy resin (B),
and other components. The mixing method is not specifically limited
so long as a uniform adhesive composition is obtained. Since the
adhesive composition is preferably used in the form a solution or a
dispersion, a solvent is generally employed. Examples of the
solvents include alcohols such as methanol, ethanol, isopropyl
alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol,
benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol
monomethyl ether, diethylene glycol monomethyl ether, and diacetone
alcohol; ketones such as acetone, methyl ethyl ketone, methyl
isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone;
aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and
mesitylene; esters such as methyl acetate, ethyl acetate, ethylene
glycol monomethyl ether acetate, and 3-methoxybutyl acetate; and
aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and
methylcyclohexane. These solvents may be used alone or in
combination of two or more. When the adhesive composition is a
solution or a dispersion (resin varnish) containing a solvent, the
application to the base film and the formation of the adhesive
layer can be smoothly carried out to readily obtain an adhesive
layer at a desired thickness.
When the adhesive composition contains a solvent, the solid
concentration is preferably from 3 to 80 mass %, and more
preferably 10 to 50 mass %, from the viewpoint of, for example,
workability including formation of the adhesive layer. If the solid
concentration is 80 mass % or less, a solution with a favorable
viscosity can be obtained to facilitate uniform coating.
(3) The Laminate Having an Adhesive Layer
An embodiment of the laminate having an adhesive layer according to
the present invention includes a coverlay film. A coverlay film
comprises the aforementioned adhesive layer which is formed on at
least one of the surfaces of a base film, and the adhesive layer
cannot be easily peeled off from the base film.
The coverlay film can be produced, for example, by coating a
surface of a base film such as a polyimide film with a resin
varnish containing the above adhesive composition and a solvent to
form a resin varnish layer, and then removing the solvent from the
resin varnish layer to obtain a coverlay film having an adhesive
layer in B stage. Herein, the "adhesive layer in B stage" refers to
a semi-cured state in which a part of the adhesive composition
starts curing, so that the curing of the adhesive composition
further proceeds by heating or the like.
The drying temperature to remove the solvent is preferably from 40
to 250.degree. C., and more preferably from 70 to 170.degree. C.
The drying process is carried out by passing the laminate having
the adhesive composition coated thereon through a furnace in which
hot air drying, far infrared heating, high frequency induction
heating or the like is carried out.
Furthermore, if necessary, a release film may be laminated onto the
surface of the adhesive layer for preservation and the like.
Examples of the release film include those known in the art, such
as a polyethylene terephthalate film, a polyethylene film, a
polypropylene film, a silicone-treated release paper, a polyolefin
resin-coated paper, a TPX film, and a fluororesin film.
Another embodiment of the laminate having an adhesive layer
includes a bonding sheet. The bonding sheet comprises the
aforementioned adhesive layer formed on the surface of a release
film (base film). In another embodiment of the bonding sheet, the
adhesive layer may be incorporated between two release films. The
release film is peeled off when the bonding sheet is used. Examples
of the release film are those mentioned above.
The bonding sheet can be produced by, for instance, coating the
surface of a release film with a resin varnish containing the
adhesive composition and a solvent, followed by drying in the same
manner as in the case of the aforementioned coverlay film.
The thickness of the adhesive layer in B stage is preferably from 5
to 100 .mu.m, more preferably from 10 to 70 .mu.m, and still more
preferably 10 to 50 .mu.m.
Although the thicknesses of the above base film and adhesive layer
are selected depending on usage, the base film tend to be thinner
to improve electrical properties. In general, warpage of the
laminate having an adhesive layer tends to occur and impairs
workability with decreasing the thickness of the base film and
increasing the thickness of the adhesive layer. However, the
laminate having an adhesive layer according to the present
invention hardly causes the warpage of the laminate even when the
base film is thin and the adhesive layer is thick. In the laminate
having an adhesive layer according to the present invention, the
ratio of the thickness of the adhesive layer (A) to the thickness
of the base film (B), i.e., (A/B), is preferably not less than 1
and not more than 10, and more preferably not less than 1 and not
more than 5. Further, it is preferred that the thickness of the
adhesive layer is larger than the thickness of the base film.
It is preferred that the warpage of the laminate having an adhesive
layer is as small as possible because the warpage affects
workability in the production process of FPC-related products. More
specifically, when a square-shaped laminate having an adhesive
layer is placed on a horizontal surface with the adhesive layer
facing up, the ratio (H/L) wherein H is an elevation of an edge of
the laminate and L is a side length of the laminate is preferably
less than 0.05. The ratio is more preferably less than 0.04, and
still more preferably less than 0.03. When the ratio (H/L) is less
than 0.05, a laminate with excellent workability can be obtained
because the warpage or curling of the laminate can be
suppressed.
Additionally, the lower limit of the H/L is 0, i.e., when H is
0.
The laminate having the adhesive layer preferably yields a
dielectric constant (.epsilon.) lower than 3.0 and a dielectric
loss tangent (tan .delta.) lower than 0.01 when measured at a
frequency of 1 GHz after the adhesive layer of the laminate is
cured. More preferably, the dielectric constant is 2.9 or lower,
and the dielectric loss tangent is 0.005 or lower. The laminate can
be favorably used in FPC-related products which must meet strict
electrical property requirements so long as the laminate yields a
dielectric constant lower than 3.0 and a dielectric loss tangent
lower than 0.01. Since the dielectric constant and the dielectric
loss tangent can be adjusted by the type and content of the
adhesive component or the type of the base film and the like,
various types of laminates can be designed depending on the usage.
The method of measuring the dielectric constant and the dielectric
loss tangent is described hereinafter.
Furthermore, it is preferred that the laminate having the adhesive
layer yields a dielectric constant (.epsilon.) of 2.2 or more and a
dielectric loss tangent (tan .delta.) of 0 or more as measured at a
frequency of 1 GHz after the adhesive layer of the laminate is
cured.
2. Flexible Copper Clad Laminate
The flexible copper clad laminate according to the present
invention is characterized in that a base film and a copper foil
are bonded to each other using the aforementioned laminate having
an adhesive layer. That is, the flexible copper clad laminate
according to the present invention comprises a base film, an
adhesive layer, and a copper foil in this order. The adhesive layer
and the copper foil may be formed on both surfaces of the base
film. Since the adhesive composition for use in the present
invention is excellent in adhesion to articles containing copper,
the flexible copper clad laminate according to the present
invention is provided as an integrated product excellent in
stability.
The method for producing the flexible copper clad laminate
according to the present invention includes, for instance, a method
in which the surface of the adhesive layer of the laminate is
brought in contact with the copper foil, hot lamination is carried
out at from 80 to 150.degree. C., and then the adhesive layer is
cured by after-curing. The after-curing conditions can be, for
example, at from 100 to 200.degree. C. for from 30 minutes to 4
hours. There is no particular limitation on the copper foil, and
usable are electrolytic copper foil, rolled copper foil, and the
like.
3. Flexible Flat Cable (FFC)
The flexible flat cable according to the present invention is
characterized in that a base film and a copper wiring are bonded to
each other using the aforementioned laminate having an adhesive
layer. That is, the flexible flat cable according to the present
invention comprises a base film, an adhesive layer, and a copper
wiring in this order. The adhesive layer and the copper wiring may
be formed on both surfaces of the base film. Since the adhesive
composition for use in the present invention is excellent in
adhesion to articles containing copper, the flexible flat cable
according to the present invention is provided as an integrated
product excellent in stability.
The method for producing the flexible flat cable according to the
present invention includes, for instance, a method in which the
adhesive layer of the laminate is brought in contact with the
copper wiring, hot lamination is carried out at from 80 to
150.degree. C., and then the adhesive layer is cured by
after-curing. The after-curing condition can be, for example, at
from 100 to 200.degree. C. for from 30 minutes to 4 hours. There is
no particular limitation on the shape of the copper wiring, so the
shape and the like can be properly selected as desired.
EXAMPLES
The present invention is explained in further detail by way of
Examples below, but the present invention is not limited thereto.
In the explanation below, parts and % are on mass basis unless
otherwise stated.
1. Evaluation Method
(1) Molecular Weight
Instrument: Alliance2695 (manufactured by Waters)
Column: 2 columns of TSK gel SuperMultiporeHZ-H 2 columns of TSK
gel SuperHZ2500 (manufactured by Tosoh Corporation)
Column temperature: 40.degree. C.
Carrier solvent: Tetrahydrofuran 0.35 ml/min
Detector: RI (Differential Refractive Index Detector)
The molecular weight measured by GPC was converted based on
polystyrene molecular weight standard.
(2) Warpage
A 25-.mu.m thick polyimide film (200 mm length.times.200 mm width)
was prepared, and the liquid adhesive compositions listed in Tables
1 and 2 were each applied by roll-coating to one of the surfaces of
the film. The coated film was then allowed to stand still in an
oven, and was dried at 90.degree. C. for 3 minutes to form a
25-.mu.m thick adhesive layer in B stage to obtain a coverlay film
A1 (a 50-.mu.m thick laminate having the adhesive layer). The
resulting coverlay film A1 was placed on a horizontal plane with
the adhesive layer facing upward, and the elevation in the vertical
direction was measured at each of the four corners. The
thus-measured elevations at the four corners were averaged, and the
ratio of the average elevation (H) to the side length (L) of the
laminate, i.e., H/L, was obtained and used to evaluate the
warpage.
Further, a coverlay film B1 (a 50-.mu.m thick laminate having the
adhesive layer) was prepared in the same manner as above, except
for changing the thickness of the polyimide film to 12.5 .mu.m and
the thickness of the adhesive layer to 37.5 .mu.m, and was
subjected to evaluation.
<Evaluation Criteria>
.circleincircle.: H/L is lower than 0.020
.smallcircle.: H/L is 0.030 or more and lower than 0.05
x: H/L is 0.10 or more
(3) Peel Adhesion Strength
A 25-.mu.m thick polyimide film was prepared, and the liquid
adhesive compositions listed in Tables 1 and 2 were each applied by
roll-coating to one of the surfaces of the film. The coated film
was then allowed to stand still in an oven, and was dried at
90.degree. C. for 3 minutes to form a 25-.mu.m thick adhesive layer
in B stage to obtain a coverlay film (a laminate having the
adhesive layer). Then, a 35-.mu.m thick rolled copper foil was
brought into surface contact with the surface of the adhesive layer
of the coverlay film, and the resultant was subjected to lamination
under a temperature of 120.degree. C., a pressure of 0.4 MPa, and a
speed of 0.5 m/minute. Then, the resulting laminate (polyimide
film/adhesive layer/copper foil) was subjected to hot pressing at a
temperature of 180.degree. C. and a pressure of 3 MPa for 30
minutes to obtain a flexible copper clad laminate A. The
thus-obtained flexible copper clad laminate A was cut into a
specified size to prepare an adhesion test piece.
Further, a flexible copper clad laminate B was prepared in the same
manner as above, except for changing the thickness of the polyimide
film to 12.5 .mu.m and the thickness of the adhesive layer to 37.5
.mu.m, to prepare an adhesion test piece.
In accordance with JIS C 6481 "Test methods of copper-clad
laminates for printed wiring boards", adhesiveness was evaluated by
measuring a 180.degree. peel adhesion strength (N/mm) when the
copper foil of each adhesion test piece was peeled off from the
polyimide film under a temperature of 23.degree. C. and a tensile
speed of 50 mm/minute. The width of the adhesion test piece at the
time of measurement was 10 mm.
(4) Solder Heat Resistance
The test was conducted in accordance with JIS C 6481 "Test methods
of copper-clad laminates for printed wiring boards". The adhesion
test pieces were each cut into 25-mm square, and were subjected to
heat treatment at 120.degree. C. for 30 minutes. Then, with the
polyimide film facing up, the adhesion test pieces were floated on
a solder bath for 10 seconds at a predetermined temperature to
observe foaming on the surface of the adhesion test pieces. The
maximum temperature at which no foaming was observed on the
adhesion test piece was taken as the temperature of solder heat
resistance.
(5) Resin Flow
A 25-.mu.m thick polyimide film was prepared, and the liquid
adhesive compositions listed in Tables 1 and 2 were each applied by
roll-coating to one of the surfaces of the film. The coated film
was then allowed to stand still in an oven, and was dried at
90.degree. C. for 3 minutes to form a 25-.mu.m thick adhesive layer
in B stage to obtain a coverlay film (a laminate having the
adhesive layer). Then, after punching a hole of 6-mm in diameter
from the surface of the adhesive layer in the coverlay film, a
35-.mu.m thick rolled copper foil was layered thereon, and the
resultant was subjected to lamination under a temperature of
120.degree. C., a pressure of 0.4 MPa, and a speed of 0.5 m/minute.
The resulting laminate A (polyimide film/adhesive layer/copper
foil) was subjected to hot pressing at a temperature of 180.degree.
C. and a pressure of 3 MPa for 30 minutes. In this instance, the
maximum length of the adhesive protruding into the hole of the
polyimide was measured. It was determined that the shorter the
protruding length was, the better the resin flow was, and the
greater the protruding length was, the worse the resin flow
was.
Further, a laminate B was prepared and evaluated in the same manner
as above, except for changing the thickness of the polyimide film
to 12.5 .mu.m and the thickness of the adhesive layer to 37.5
.mu.m.
(6) Electrical Properties (Dielectric Constant and Dielectric Loss
Tangent)
A 25-.mu.m thick polyimide film was prepared, and the liquid
adhesive compositions listed in Tables 1 and 2 were each applied by
roll-coating to one of the surfaces of the film. The coated film
was then allowed to stand still in an oven, and was dried at
90.degree. C. for 3 minutes to form a 25-.mu.m thick adhesive layer
in B stage to obtain a coverlay film A2 (a 50-.mu.m thick laminate
having the adhesive layer). The resulting coverlay film A2 was then
allowed to stand still in an oven, and was heated and cured at
180.degree. C. for 30 minutes to obtain a test piece of 120
mm.times.100 mm in size.
Further, a coverlay film B2 (a 50-.mu.m thick laminate having the
adhesive layer) was prepared in the same manner as above, except
for changing the thickness of the polyimide film to 12.5 .mu.m and
the thickness of the adhesive layer to 37.5 .mu.m. The resultant
was subjected to heat curing treatment at 180.degree. C. for 30
minutes to obtain a test piece of 120 mm.times.100 mm in size.
The dielectric constant (.epsilon.) and the dielectric loss tangent
(tan .delta.) of the laminate having an adhesive layer were
measured using a network analyzer 85071E-300 (manufactured by
Agilent Technologies, Inc.) in accordance with the split post
dielectric resonator (SPDR) method, at a temperature of 23.degree.
C. and at a frequency of 1 GHz.
(7) Storage Stability of the Laminate Having an Adhesive Layer
A coverlay film A2 (a 50-.mu.m thick laminate having the adhesive
layer) prepared in the same manner as in the aforementioned (6)
"Electrical properties" was stored at 23.degree. C. for a
predetermined duration of time, and the coverlay film A2 after
storage was subjected to hot pressing with a copper single-sided
board (L/S=50 .mu.m/50 .mu.m, having copper thickness of 18 .mu.m)
at a temperature of 180.degree. C. and a pressure of 3 MPa for 3
minutes to evaluate a filling property of the resin. The storage
period of time at which the resin no longer fills in the substrate
was taken for evaluation.
<Evaluation Criteria>
.smallcircle.: 2 months or longer
.DELTA.: 1 week or longer and less than 1 month
x: less than 1 week
2. Raw Materials of the Adhesive Composition
2-1. Styrene-Based Resin
(1) Styrene-Based Elastomer a1
A maleic acid modified styrene-ethylenebutylene-styrene block
copolymer "TUFTEC M1913" (a trade name of a product manufactured by
Asahi Kasei Corporation) was used. The acid value of the copolymer
is 10 mg KOH/g, the styrene/ethylenebutylene ratio is 30/70, and
the weight average molecular weight is 150,000.
(2) Styrene-Based Elastomer a2
A maleic acid modified styrene-ethylenebutylene-styrene block
copolymer "TUFTEC M1911" (a trade name of a product manufactured by
Asahi Kasei Corporation) was used. The acid value of the copolymer
is 2 mg KOH/g, the styrene/ethylenebutylene ratio is 30/70, and the
weight average molecular weight is 150,000.
(3) Styrene-Based Elastomer .alpha.
A styrene-ethylenebutylene-styrene block copolymer "TUFTEC H1041"
(a trade name of a product manufactured by Asahi Kasei Corporation)
was used. The acid value of the copolymer is 0 mg KOH/g, the
styrene/ethylenebutylene ratio is 30/70, and the weight average
molecular weight is 150,000.
(4) Styrene-Containing Oligomer
"OPE-St resin" (trade name) manufactured by Mitsubishi Gas Chemical
Company, Inc., was used.
2-2. Epoxy Resin
(1) Epoxy Resin b1
An epoxy resin having a dicyclopentadiene structure, "EPICLON
HP-7200" (trade name) manufactured by DIC Corporation, was
used.
(2) Epoxy Resin b2
A cresol novolac epoxy resin, "EPICLON N-655 EXP" (trade name),
manufactured by DIC Corporation, was used.
(3) Epoxy Resin b3
A glycidylamino based epoxy resin, "TETRAD-C" (trade name),
manufactured by Mitsubishi Gas Chemical Company, Inc., was
used.
2-3. Others
(1) Curing Accelerator
An imidazole-based curing accelerator "CURESOL C11-Z" (trade name),
manufactured by Shikoku Chemicals Corporation was used.
(2) Inorganic Filler 1
Silica, "EXCELICA SE-1" (trade name), manufactured by Tokuyama
Corporation was used.
(3) Inorganic Filler 2
"OP-935" (trade name), manufactured by Clariant Japan was used.
(4) Solvent
A mixed solvent constituted by toluene and methyl ethyl ketone at a
mass ratio of 90:10 was used.
3. Preparation of the Adhesive Composition
The above raw materials were put into a 1000-ml flask equipped with
a stirrer in the proportion shown in Tables 1 and 2, and were
dissolved under stirring for 6 hours at room temperature to obtain
a liquid adhesive composition containing 20% of solid content.
4. Preparation and Evaluation of the Laminate Having an Adhesive
Layer
Examples 1 to 8 and Comparative Examples 1 to 5
Laminates having an adhesive layer were each prepared using the
above adhesive compositions, and were subjected to evaluation. The
results are given in Tables 1 and 2.
TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 Adhesive
Styrene-based elastomer a1 100 100 100 100 100 100 80 Composition
Styrene-based elastomer a2 100 (parts by mass) Styrene-containing
oligomer 20 Epoxy resin b1 6 7 5 15 6 4 Epoxy resin b2 6 Epoxy
resin b3 6 Curing accelerator 0.2 0.2 0.2 0.5 0.2 0.2 0.2 0.2
Inorganic filler 1 15 Inorganic filler 2 30 Solvent 400 400 450 450
400 400 400 400 Results of Warpage of coverlay film A1
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.c- ircleincircle. .circleincircle. .largecircle. .circleincircle.
Evaluation Peel adhesion strength of flexible copper 1.0 1.3 0.9
0.9 1.0 1.0 1.0 1.4 clad laminate A (N/mm) Solder heat resistance
of flexible copper 360 360 330 360 360 360 360 300 clad laminate A
(.degree. C.) Resin flow of laminate A (mm) 0.20 0.05 0.05 0.15
0.15 0.20 0.10 0.10 Dielectric constant (.epsilon.) of coverlay
film A2 2.8 2.9 2.9 2.9 2.9 2.8 2.9 2.8 Dielectric loss tangent
(tan .delta.) of coverlay 0.004 0.004 0.005 0.004 0.005 0.004 0.005
0.004 film A2 Storage stability of coverlay film A2 .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. - .DELTA.
.largecircle. .largecircle. Warpage of coverlay film B1
.circleincircle. .largecircle. .largecircle. .circleincircle.
.circlei- ncircle. .circleincircle. .largecircle. .circleincircle.
Peel adhesion strength of flexible copper 1.1 1.5 1.0 1.0 1.1 1.1
1.1 1.6 clad laminate B (N/mm) Solder heat resistance of flexible
copper 360 360 330 360 360 360 360 300 clad laminate B (.degree.
C.) Resin flow of laminate B (mm) 0.25 0.15 0.2 0.2 0.2 0.25 0.15
0.15 Dielectric constant (.epsilon.) of coverlay film B2 2.6 2.7
2.7 2.6 2.7 2.6 2.7 2.6 Dielectric loss tangent (tan .delta.) of
coverlay 0.003 0.003 0.005 0.004 0.005 0.003 0.005 0.003 film
B2
TABLE-US-00002 TABLE 2 Comparative Examples 1 2 3 4 5 Adhesive
Styrene-based elastomer a1 50 100 100 Composition Styrene-based
elastomer .alpha. 50 100 (parts by mass) Styrene-containing
oligomer 50 50 Epoxy resin b1 6 6 25 50 7 Curing accelerator 0.2
0.2 1 2 0.2 Inorganic filler 2 30 Solvent 450 450 450 500 400
Results of Warpage of coverlay film A1 X X .largecircle.
.largecircle. .circleincircle. Evaluation Peel adhesion strength of
flexible copper clad laminate A (N/mm) 1.1 1.1 0.4 0.3 0.6 Solder
heat resistance of flexible copper clad laminate A (.degree. C.)
330 360 360 360 260 Resin flow of laminate A (mm) 0.10 0.10 0.20
0.05 0.75 Dielectric constant (.epsilon.) of coverlay film A2 3.0
3.0 3.0 3.1 2.8 Dielectric loss tangent (tan .delta.) of coverlay
film A2 0.005 0.005 0.006 0.009 0.004 Storage stability of coverlay
film A2 .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Warpage of coverlay film B1 X X .largecircle.
.largecircle. .circleincircle. Peel adhesion strength of flexible
copper clad laminate B (N/mm) 1.2 1.2 0.5 0.4 0.7 Solder heat
resistance of flexible copper clad laminate B (.degree. C.) 330 360
360 360 260 Resin flow of laminate B (mm) 0.15 0.15 0.25 0.1 0.9
Dielectric constant (.epsilon.) of coverlay film B2 2.9 2.8 2.8 2.9
2.6 Dielectric loss tangent (tan .delta.) of coverlay film B2 0.005
0.005 0.006 0.01 0.003
The results in the above Tables 1 and 2 shows that the laminates
having an adhesive layer obtained in Examples 1 to 8 exhibit little
warpage; and therefore are satisfactory in workability in
manufacturing processes of FPC-related products. Furthermore, it
can be readily understood that these laminates having an adhesive
layer show excellent adhesiveness, resin flow, and electrical
properties. On the other hand, Comparative Examples 1 and 5 in
which no carboxyl group-containing styrene-based elastomer was used
as a styrene based resin were low in adhesiveness and thermal
resistance. Further, Comparative Example 2 in which the content of
the carboxyl group-containing styrene-based elastomer was too low
suffered from warpage. Furthermore, Comparative Examples 3 and 4 in
which the content of the epoxy resin was outside the range
specified in the present invention were deficient in adhesiveness
and electrical properties.
INDUSTRIAL APPLICABILITY
The laminate having an adhesive layer according to the present
invention exhibits little warpage even when the base film is thin;
therefore the laminate is excellent in workability. Furthermore,
the laminate is suitable for producing FPC-related products because
it shows excellent adhesiveness, resin flow, and electrical
properties.
* * * * *